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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
  • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
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  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0291—Aliphatic polycarbonates unsaturated
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  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/14—Lactams
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  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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  • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
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  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
  • C09J177/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated
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  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
  • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
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  • C08G2150/00—Compositions for coatings
  • C08G2150/20—Compositions for powder coatings

Definitions

• the invention relates to a polymer which is obtainable by polycondensation or polyadduct formation from monomeric compounds, wherein accompanying use is made as monomeric compound of 1,1-dimethylolcycloalkanes of the formula I or 1,1-dimethylolcycloalkenes of the formula Ia
• Diols are needed for the preparation of polymers, examples being polyesters or polyurethanes.
• EP-A 562 578 for example, the use of various cyclohexanediols such as 1,4-cyclohexanedimethanol or 1,4-cyclohexanediethanol in the preparation of polyesters is described.
• Ullmann's Encyclopedia of Industrial Chemistry, “Alcohols, Polyhydric” by Peter Werle et al., page 4-6 describes the use of neopentylglycol instead of 1,4-cyclohexanedimethanol.
• DE-A 922648 describes a process for preparing cycloalkane-1,1-dicarboxylic acids in the course of which the 1,1-dimethylolcycloalkanes, among other species, are formed temporarily. The use of these 1,1-dimethylolcycloalkanes for preparing polymers is not disclosed.
• DE-A 1468065 describes a process for preparing a mixture of cyclododecane derivatives that comprises primarily monooxymethylcyclododecane. That process starts from cyclododecatriene, which through addition of carbon monoxide and hydrogen is subjected to a hydroformylation. Subsequently, the resultant aldehyde is subjected to a further hydrogenation to give the corresponding alcohol. According to this method of preparation, however, only one methylol group is introduced per double bond. A preparation of a dimethylol derivative with both methylol groups at the same C atom is not described. 1,1-Dimethylolcyclodecane, and its use for preparing polymers, is not described.
• the viscosity is of particular importance, whether as the melt viscosity (100% systems) or the solution viscosity (polymer solutions).
• the coatings produced are to have good mechanical properties, such as impact toughness and elasticity, high scratch resistance and impact resistance, high resistances to water, solvents, grease and chemicals and environmental influences and also a high gloss.
• the polymers are to have a high weather stability and a relatively low propensity toward yellowing.
• X is —CH 2 — or —O—
• R is hydrogen or a linear or branched alkyl group having 1 to 10 C atoms, and, for the compounds of the formula Ia, when n is ⁇ 2, there may also be more than one double bond present.
• X is —CH 2 —
• R is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and n-pentyl.
• the compounds of the formula I or of the formula Ia are obtainable by reacting aldehydes of the formula II or of the formula IIa
• n, X, and R have the preceding definition, with formaldehyde in a Cannizzaro reaction.
• the polymer of the invention is a polyester.
• the polymer is a polycarbonatediol (obtainable by reacting dialkyl carbonates or cyclic carbonates with diols, with elimination of alcohol).
• the polymer is a polyurethane.
• the polymer is a polyadduct which is obtainable by ring-opening addition polymerization of lactones or lactams.
• the invention further provides for the use of the polymer of the invention for preparing a thermoplastic composition.
• the invention further provides a thermoplastic composition comprising a polymer of the invention and/or repeat units of a polymer of the invention.
• the invention further provides for the use of the thermoplastic compositions of the invention for producing shaped articles.
• the invention further provides for the use of the polymer of the invention for preparing coating materials, sealants or adhesives.
• the invention further provides coating materials, sealants or adhesives comprising repeat units of a polymer of the invention.
• the coating materials, sealants or adhesives of the invention advantageously comprise aqueous materials.
• the invention further provides for the use of a polymer of the invention for producing powder coating materials.
• the invention further provides powder coating materials comprising repeat units of a polymer of the invention.
• the invention further provides for the use of a polymer of the invention for producing radiation-curable coating materials.
• the invention further provides radiation-curable coating materials comprising repeat units of a polymer of the invention.
• the invention further provides 1,1-dimethylolcyclododecane.
• the invention further provides a process for preparing 1,1-dimethylolcyclododecane, by subjecting cyclododecene to hydroformylation with hydrogen and carbon monoxide, and reacting the resulting aldehyde by means of formaldehyde to give 1,1-dimethylolcyclododecane.
• the invention further provides a mixture comprising 1,1-dimethylolcyclooct-3-ene, 1,1-dimethylolcyclooct-2-ene, and 1,1-dimethylolcyclooct-4-ene.
• the invention further provides a process for preparing the mixture comprising 1,1-dimethylolcyclooct-3-ene, 1,1-dimethylolcyclooct-2-ene, and 1,1-dimethylolcyclooct-4-ene by subjecting 1,5-cyclooctadiene to a hydroformylation with hydrogen and carbon monoxide and reacting the resultant aldehydes by means of formaldehyde to give the mixture of the invention.
• the polymers of the invention are prepared using compounds of the formula I or of the formula Ia or the alkoxylated derivatives of the formula I or of the formula Ia in which n is a whole natural number selected from the group consisting of 1, 2, and 4 to 9. More preferably n is 2, 5 or 9; very preferably n is 2.
• the radical R is selected from the group consisting of hydrogen or a linear or branched alkyl group having 1 to 10 C atoms; more preferably R is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and n-pentyl; very preferably R is hydrogen.
• X is either a CH 2 group or oxygen. More preferably X is a CH 2 group. Particular preference is given to compounds of the formula I or of the formula Ia in which n is 2, 5 or 9, R is hydrogen or methyl, and X is a CH 2 group. Very particular preference is given to 1,1-dimethylolcyclopentane as compound of the formula I and dimethylolcyclopentene as compound of the formula Ia.
• the alkoxylated derivatives of the compound of the general formula I or of the formula Ia are products of the reaction with one or with a mixture of alkylene oxides.
• alkylene oxides are ethylene, propylene, n-butylene, isobutylene, styrene or cyclohexene oxides. More particularly the aforementioned diols are ethoxylated and propoxylated.
• the alkoxylation products are obtainable in a known way by reaction of the above alcohols with alkylene oxides, especially ethylene oxide or propylene oxide.
• the degree of alkoxylation per hydroxyl group is preferably 0 to 20, more particularly 0 to 10, i.e., 1 mol of hydroxyl group may be alkoxylated preferably with up to 20 mol, more particularly 10 mol, of alkylene oxides.
• the compounds of the formula I or of the formula Ia are not alkoxylated.
• the compounds of the formula I or of the formula Ia are obtained by a Cannizzaro reaction of the corresponding aldehyde of the formula II or of the formula IIa with formaldehyde.
• the process for preparing 1,1-dimethylolcycloalkanes is already known and is described in U.S. Pat. No. 2,993,912 or DE 922648.
• compounds of the formula I or formula Ia may be obtained by aldol reaction of the corresponding aldehydes of the formula II or of the formula IIa with formaldehyde followed by hydrogenation.
• the aldol reaction is described in, for example, WO 01/51438, WO 97/17313 or WO 98/29374.
• the hydrogenation can be carried out by analogy with the disclosure in EP-A 44412 or EP-A 44444.
• the polymers are obtainable by polycondensation or polyadduct formation from monomeric compounds with accompanying use of one or more compounds of the formula I or of the formula Ia; the polymers can, if desired, be chemically modified—for example, functionalized or crosslinked—by other or further reactions.
• Preferred polycondensates are polyesters, which are obtainable by reacting diols or polyols with dicarboxylic or polycarboxylic acids, which can also be used in the form of reactive derivatives, such as anhydrides or esters.
• polyester is intended below to refer to a polymer which is composed to an extent of more than 50%, more preferably more than 70%, and more particularly more than 90% by weight of synthesis components selected from diols, polyols, dicarboxylic acids and polycarboxylic acids.
• polycarbonate diols which are obtainable by reacting dialkyl carbonates or cyclic carbonates with diols, with elimination of alcohols.
• polyurethane As a polyadduct, mention may be made in particular of polyurethane. In particular it is possible for polyurethanes also to comprise repeat units of polymers of the invention.
• polyadducts which are obtainable by ring-opening addition polymerization of lactones or lactams.
• polyurethane is intended below to refer to a polymer which is composed to an extent of more than 50%, more preferably more than 70%, and more particularly more than 90% by weight of synthesis components selected from diisocyanates, polyisocyanates, diols and polyols.
• Preferred polymers are polyesters and polyurethanes; polyesters are particularly preferred.
• the polymers of the invention preferably have the below-stated content of the monomer units of the compounds of the formula I or of the formula Ia or alkoxylated derivatives thereof.
• the below-stated weight figures relating to the amount of the compounds of the formula I or of the formula Ia or alkoxylated derivatives thereof in the polymer refer in this case to the units of the polymer that derive from compounds of the formula I or of the formula Ia or their alkoxylated compounds.
• the weight of these units corresponds directly to the compound of the formula I or of the formula Ia or alkoxylated derivatives thereof; in the case of polycondensates, the weight of these units is reduced in value by the weight of the hydrogen atoms of the hydroxyl groups.
• Preferred polymers are composed to an extent of at least 0.5%, more preferably at least 2%, very preferably at least 5%, and more particularly at least 10% by weight and in one particular embodiment at least 20% by weight, of compounds of the formula I or of the formula Ia or their alkoxylated derivatives. Since the accompanying use of other compounds reactive with the diols is mandatory, the polymers are generally composed to an extent of not more than 90%, more particularly not more than 60%, or not more than 50%, by weight, of the compounds of the formula I or of the formula Ia or their alkoxylated derivatives.
• the polymers may also comprise other diols or polyols as synthesis components.
• at least 10%, more preferably at least 25%, and very preferably at least 50% by weight of the diols and polyols of which the polymers are composed comprise the compounds of the formula I or of the formula Ia or their alkoxylated derivatives.
• At least 70% by weight or at least 90% by weight of the diols and polyols, of which the polymers are composed may comprise the compounds of the formula I or of the formula Ia or their alkoxylated derivatives.
• 100% by weight of all the diols and polyols of which the polymers are composed may comprise a single compound of the formula I or of the formula Ia or may comprise a mixture of compounds of the formula I or of the formula Ia or their alkoxylated derivatives.
• Polyesters besides the compounds of the formula I or of the formula Ia or their alkoxylated derivatives, may comprise further diols or polyols as synthesis components.
• Examples of further diols include ethylene glycol, propylene glycol and their counterparts with higher degrees of condensation, such as, for example, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol etc., 2-methyl-1,3-propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, alkoxylated phenolic compounds, such as ethoxylated and/or propoxylated bisphenols, and cyclohexanedimethanol.
• diethylene glycol triethylene glycol
• dipropylene glycol tripropylene glycol etc.
• 2-methyl-1,3-propanediol butanediol
• pentanediol hexanediol
• neopentyl glycol alkoxylated phenolic compounds, such as ethoxylated and/or propoxyl
• polystyrene resin examples include glycerol, trimethylolpropane, butanetriol, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, and mannitol.
• glycerol trimethylolpropane
• butanetriol trimethylolethane
• pentaerythritol ditrimethylolpropane
• dipentaerythritol dipentaerythritol
• sorbitol mannitol
• Preferred mixtures of the compounds of the formula I or of the formula Ia with a diol and a triol are mixtures of the unsubstituted 5-, 8-, 10- and 12-membered rings, carrying CH 2 group as X, with neopentylglycol and trimethylolpropane.
• the above diols or polyols may be alkoxylated, more particularly ethoxylated and propoxylated.
• the alkoxylation products are obtainable in a known way by reaction of the above alcohols with alkylene oxides, especially ethylene oxide or propylene oxide.
• the degree of alkoxylation per hydroxyl group is preferably 0 to 20, more particularly 0 to 10, i.e., 1 mol of hydroxyl group may be alkoxylated preferably with up to 20 mol of alkylene oxide.
• the polyesters further comprise dicarboxylic acids or polycarboxylic acids as synthesis components.
• dicarboxylic acids or polycarboxylic acids may also be used in the form of their reactive derivatives, e.g. as anhydrides or esters.
• Suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, isophthalic acid, terephthalic acid, their isomers and hydrogenation products, such as tetrahydrophthalic acid.
• maleic acid and fumaric acid for unsaturated polyesters.
• Polyesters may also comprise monoalcohols or monocarboxylic acids as a constituent; through accompanying use of compounds of this kind it is possible to adjust or limit the molecular weight.
• the polyesters may comprise particular functional groups.
• Water-soluble or water-dispersible polyesters comprise the necessary amount of hydrophilic groups, carboxyl groups or carboxylate groups, for example, to achieve solubility in water or dispersibility in water.
• Crosslinkable polyesters, for powder coating materials for example comprise functional groups, which enter into a crosslinking reaction with the crosslinking agent that is used. These may likewise be carboxylic acid groups, if crosslinking is intended with compounds comprising hydroxyl groups, hydroxyalkylamides, for example.
• the functional groups may also be ethylenically unsaturated groups, through modification of the polyester with unsaturated dicarboxylic acids (maleic acid) or reaction with (meth)acrylic acid, for example.
• Polymers of this kind are radiation curable or crosslinkable chemically or thermally.
• Unsaturated polyesters may also be copolymerized with free-radically polymerizable compounds that contain single or else multiple ethylenic unsaturation, such as styrene, C 1 -C 10 alkyl acrylates, dialkyl acrylates, e.g. the diacrylate of ethanediol or butanediol.
• the unsaturated polyester may be used in a mixture with the ethylenically unsaturated monomers, as described in WO 00/23495 and EP 1131372, for example.
• the above ethylenically unsaturated compounds serve simultaneously as solvents (reactive diluents), and so the mixture is present preferably as a solution of the polyesters in these compounds.
• the mixture may be used, for example as a coating or impregnating composition, including in particular its use for producing laminates. Curing may take place thermally or photochemically, in both cases also optinally with addition of an initiator.
• Compounds of this kind which can be cured chemically, thermally or by UV irradiation are specific thermoplastics, which are also called thermosets.
• unsaturated compounds of the formula I or of the formula Ia are suitable more particularly for UPR (unsaturated polyester resins)
• Polyurethanes comprise di- or polyisocyanates as an essential synthesis component.
• diisocyanates Y(NCO)2 where Y is an aliphatic hydrocarbon radical having 4 to 15 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
• diisocyanates of this kind are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis(4-isocyanatocyclohexyl)propane, trimethylhexane diisocyanate, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4′-diisocyanatodiphenylmethane, 2,4′-diisocyanato-diphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis(4-iso
• Particularly important mixtures of these isocyanates are the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane; a particularly suitable mixture is that of 80 mol % of 2,4-diisocyanatotoluene and 20 mol % 2,6-diisocyanatotoluene.
• aromatic isocyanates such as 2,4-diisocyanatotoluene and/or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI, the preferred mixing ratio of aliphatic to aromatic isocyanates being 4:1 to 1:4.
• the invention uses compounds of the general formula I or of the formula Ia as pure compounds or as mixtures of compounds of the general formula I or of the formula Ia or in a mixture with other diols or polyols.
• diols and/or polyols it is also possible more particularly to use polymers of the invention.
• polyester diols and/or polyester polyols as diols and/or polyols. They are referred to in general below as polyesterols.
• polyesterols are obtained beforehand by reacting diols or polyols with dicarboxylic or polycarboxylic acids (see above description of the polyesters).
• the compounds of the general formula I or of the formula Ia or mixtures of compounds of the general formula I or of the formula Ia may be comprised in the polyurethanes in the form of such polyesterols.
• diols and polyols contemplated are those mentioned above, either as synthesis components which are reacted directly with the di- or polyisocyanates, or as a constituent of the polyesterols.
• Suitable dicarboxylic acids or polycarboxylic acids for the polyesterols are likewise those mentioned above.
• the polyurethanes may also comprise monoalcohols or monoisocyanates as constituents; by accompanying use of such compounds it is possible to adjust or limit the molecular weight.
• the polyurethanes may comprise particular functional groups.
• Water-soluble or water-dispersible polyurethanes comprise the necessary amount of hydrophilic groups, carboxyl groups or carboxylate groups, for example, to achieve solubility in water or dispersibility in water.
• An example of a suitable synthesis component is dimethylolpropionic acid.
• Crosslinkable polyurethanes comprise functional groups, which enter into a crosslinking reaction with the crosslinking agent that is used. Beside urethane groups, the polyurethanes may more particularly also comprise other functional groups, urea groups, for example, which form through reaction of the di- or polyisocyanates with amino compounds.
• the polymers may, if desired, be chemically modified—for example, functionalized or crosslinked—by other or further reactions during or else, in particular, at a later point in time, as for example in the course of their use.
• the polymers may comprise crosslinking groups which, as soon as the necessary conditions are present, enter into a crosslinking reaction, and thus act as thermosets.
• the polymers may, in particular, also be used in a mixture with crosslinkers which at the desired point in time, and under the necessary conditions (more particularly at an elevated temperature), enter into a crosslinking reaction with the polymer.
• the crosslinker is not added until shortly before the subsequent use; in the case of 1K systems, the crosslinker may be added to the system at an early stage (latent crosslinker), with crosslinking occurring only under the conditions that are brought about later on, such as during the removal of solvents and/or during an increase in temperature, for example.
• laminate crosslinker early crosslinker
• Typical crosslinkers are, for example, isocyanates, epoxides, acid anhydrides or else—in the case of polymers having free radically polymerizable ethylenically unsaturated groups—ethylenically unsaturated monomers such as styrene.
• the polymers are suitable for use as a constituent of thermoplastic compositions.
• the polymers, polyesters or polyurethanes, for example, have for this purpose, preferably a sufficiently high molecular weight to give them thermoplastic properties.
• Thermoplastic compositions are generally used for producing shaped articles, in which context it is possible to employ customary methods such as injection molding, extrusion or blow molding.
• polymers are suitable for use as a constituent of coating materials, sealants or adhesives.
• the coating materials, sealants or adhesives comprise the polymers of the invention preferably as binders. They may comprise further binders and other additives, examples being antioxidants, stabilizers, dyes, pigments, flow control assistants, thickeners, or wetting assistants.
• the coating materials, sealants or adhesives may be aqueous or solventborne materials.
• Aqueous materials are preferred.
• Materials of this kind comprise the binders of the invention preferably in the form of solutions or dispersions in water or organic solvents or mixtures thereof.
• the polymers comprise additional functional groups which produce solubility or dispersibility in water or organic solvents, preferably in water (see above).
• the coating materials, sealants or adhesives may also be materials which are largely free of water or organic solvents (known as 100% systems).
• Materials of this kind generally comprise less than 10 parts by weight of water or other organic solvents (boiling point less than 150° C. at 1 bar), per 100 parts by weight of the materials. With particular preference they comprise less than 2 parts by weight, very preferably less than 1 part by weight, or less than 0.5 part by weight of water or other organic solvents (boiling point less than 150° C. at 1 bar), per 100 parts by weight of the materials.
• the materials in question may be materials which are still fluid at room temperature or may be materials which are present in the form, for example, of a powder and which are processed only at elevated temperatures.
• the materials, especially the coating materials may be radiation-curable or used as radiation-curable materials or coating materials which are referred to as thermosets.
• they preferably comprise a radiation curable polymer of the invention, more particularly a radiation-curable polyester (see above).
• the radiation curing may take place with high-energy radiation, electron beams, for example, or UV light; when UV light is used, it is possible with preference to add a photoinitiator to the polymer.
• One preferred use in the context of the present invention is the use of the polymers of the invention as or in powder coating materials.
• powder coating material it is preferred to use polyesters which are crosslinkable.
• the powder coating material is prepared by mixing and melting the polyester, crosslinker and further additives, pigments and flow control agents, for example, at high temperatures.
• the mixture can be brought into powder form by subsequent extrusion and corresponding processing of the extrudate.
• the powder may be coated onto the desired substrates, examples being those with surfaces of metal, plastic or wood, in a conventional manner, including, for example, electrostatically.
• the polymers of the invention have a low viscosity, both a low melt viscosity (100% systems) or a low solution viscosity (polymer solutions). Moreover, they have high weathering stability and very good resistance to hydrolysis. The low viscosity allows easy handling, produces good coating properties and permits higher solids fractions in solutions or dispersions or lower binder fractions in pigmented materials.
• the polymers of the invention are also, in particular highly resistant to hydrolysis.
• the polymers of the invention When used in coating materials, sealants and adhesives, the polymers of the invention produce good mechanical properties; in particular the coating materials, powder coating materials, for example, have high impact toughness, good elasticity and high gloss.
• ADA adipic acid
• DPG dipropylene glycol DBTO: dibutyltin oxide
• DSC differential scanning calorimetry
• GPC gel permeation chromatography
• IPA isophthalic acid
• M n number-average molecular weight in [g/mol]
• M w weight-average molecular weight in [g/mol]
• NVC nonvolatiles content
• NPG neopentylglycol OHN: OH number AN: acid number T g :
• the molecular weight determinations are carried out by GPC.
• Stationary phase highly crosslinked porous polystyrene-divinylbenzene, available commercially as PL-GEL from Polymer Laboratories.
• Mobile phase THF.
• Flow rate 0.3 ml/min. Calibration with polyethylene glycol 28700 to 194 daltons from PSS.
• the acid number of the polyesters is determined in accordance with the DIN standard method 53169.
• the melt viscosity ⁇ 1 of the polyesters is determined using a cone/plate viscometer at 160° C. in oscillation mode and is carried out with an angular velocity of 0.1 rad/s.
• the solution viscosity ⁇ 2 of the polyesters is determined using a cone/plate viscometer at room temperature in rotation mode.
• the solutions consist of 70% polyester and 30% solvent (5/1 mixture of Solvesso 100TM/Solvenon PMTTM).
• the Tg of the polyester is determined by means of DSC in accordance with ASTM D3418.
• the oligomer synthesized above is cooled to 180° C. and then 187.7 g of IPA (1.13 mol) are added. The temperature is raised to 230° C., and condensation is continued under these conditions until the polymer has an SN of 50 ⁇ 2 mg KOH/g.
• the water formed from the polymerization can be stripped off at the end of the reaction by a gentle vacuum, in order to achieve the desired AN.
• P1 has a glass transition temperature T g of 74° C. and a melt viscosity ⁇ 1 of 41.9 Pa*s at 160° C.
• the polymers P2 and P3, according to the invention have a significantly higher glass transition temperature than the corresponding comparative polymer P4, which represents an advantage for powder coating materials.
• polyester P5 has an AN of 10 to 15 mg KOH/g.
• P5 has an OHN of 109 mg KOH/g and a glass transition temperature T g of 23° C.
• P5 has a melt viscosity ⁇ 1 of 2.2 Pa*s at 160° C.
• the solution viscosity ⁇ 2 of the polyester P5 at room temperature (P3 solution of 70% NVC and a 5/1 mixture of Solvesso 100TM/Solvenon PMTM as solvent) is 16.3 Pa*s (see Table 2).
• the oligomer synthesized above is cooled to 160° C. and then 167.7 g of TMA (0.87 mol) are added. The temperature is raised to 230° C., and condensation is continued under these conditions until the polymer has an AN of 42 to 48 mg KOH/g.
• the water formed from the polymerization can be stripped off at the end of the reaction by a gentle vacuum, in order to achieve the desired AN.
• P8 has a glass transition temperature T g of 53° C. and a melt viscosity ⁇ 1 of 6.0 Pa*s at 160° C.
• a 20% strength aqueous colloidal solution of P8 is prepared, brought to a pH of 8 using N,N-dimethylethanolamine and stored at 45° C. The time taken for the colloidal solution to undergo precipitation is taken as a measure of the resistance of the polyester to hydrolysis (see Table 4).
• the table above shows that the polyesters comprising DMCP have a particularly high resistance to hydrolysis.
• the reference binder (REF) is the polyester resin Uralac® P-862 (T g 58.0° C., AN 35 mg KOH/g) from DSM Resins B.V.
• the reference binder (REF) is the polyester resin Uralac® P-862 (T g 58.0° C., AN 35 mg KOH/g) from DSM Resins B.V.
• 570.0 g of powder polyester P1, P4 or REF are mixed with 30.0 g of commercial curing agent Primid® XL-552 (hydroxyalkylamide from EMS), 300.0 g of titanium dioxide pigment Kronos® 2160 (Kronos), 9.0 g of flow control agent Resiflow® PV5 (Worlée Chemie GmbH) and 2.5 g of benzoin in a universal laboratory mixer (MIT Mischtechnik GmbH), and the mixture is melted and then extruded at 80-100° C. in a twin-screw extruder (MP 19, APV). The extrudate obtained is then coarse
• Test parameters Test method Flow properties Fluidizability DIN ISO 8130-5 Tableting DIN ISO 8130-11 Gel time DIN ISO8130-6
• the powder coating materials are applied to metal gradient oven panels and the panels are baked in a gradient oven (BYK-Gardner GmbH) at 160° C. for 10 minutes.
• the fully cured coatings are investigated for their visual properties (yellowing).
• the yellowness index is determined with the aid of the Spectrocolor colorimeter (Hach Lange GmbH).
• the powder coating materials are applied electrostatically to steel test panels (Q-panel R-36) and baked at 160° C. for 10 minutes.
• the target film thicknesses are from 60 ⁇ m to 80 ⁇ m.
• the resulting coatings are subjected to the following tests:
• Test parameter Test method Glass Appearance visual assessment of surfaces plates Gloss DIN EN ISO 2813 Impact sensitivity DIN 53157 Steel Impact sensitivity DIN 53157 test Elasticity DIN 53156 panels Hydrolysis resistance Daimler-Chrysler Test PBODCC371 Chemical resistance Daimler-Chrysler Test PBODCC371
• the high-solids coating materials 1K-PL5 and 1K-PL6 of the invention exhibit very good mechanical properties and high hydrolysis resistance.

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